Deformation of keratinous fibers with sulfite-borohydride composition



used at clearly defined pH- values.

'aforesaaaimaiaa: 1

. Pr p. 1 Tier-ably, I

' {-the" rediicuig 'agentsemployed being such thatth'e'concentiation-ofactive h drogen theoretically available is not more'than Z-gi'ains' P'e too-cc. of the aqueous' reducing' DEFORMATION FKERATINOUS FIBERS WITH SULFITE-BOROHYDRIDE COMPOSITION Roger Charla,Soisy-sous-Montmorency, and Gregoire Kalopissis,.Paris, France,assign-ors to Societe Anonyme (lite: Societe Monsavon-lOreal, Paris,France, a corporation of France N0 Drawing. Filed May 19, 1958,8613735,968

priority, application France May 20, 19:57

Claims. (Cl. 8-127-5) This invention relates to the deformation ofkeratinous fibers and moreespecially live human hair. The curling ordekinking of hair is eflected by means of compositions,v

effectiveness of which depends primarily upon the nature of thereducingsubstances contained therein. More especially, inorganic ororganic'sulphites, if desired inassociation with bisu-lphites, areusually employed. =Thiols or mercaptansmay also be used, generally inthe form of alkali metal'salts or anunonium salts.

Difficulties are encountered in applying the aforesaid reducing agents,and more especially since they must be of mercaptans' isfsomewhatunpleasant and they may produce allergic reactions in persons with whomthey come into contactj It has therefore previously been proposed touse, for splitting the cystine linkages of the keratin of the' hair,hydrogen-generating reactants consisting of alkali metal borohydrides,preferably as a powder. uni- Moreover, the odor forrnly embedded inawater-miscible, inert carrier as described in copendingapplication,'Serial No. 573,618, filed March 26, l956'j(now abandoned).I i I i Such a process of permanently waving hair by means ofan'aqueoussolution of an alkaline borohydride is described 'in copending'applicatiori; Serial No. 593,364, filed June 25, 1956;(now abandoned),Althoughitobviates the disadvantages inherent in the use of sulphites-ormercaptans, its application nevertheless requires ;a fairly strictcontrol of the pH value' of the medium employed,

as the basicity ofthe aqueous borohydride solutions increases along withhydrolysis; this conitrol'however is the the nature "1 the compositionto be used ffcdpeiiaijng agpliandn er1aljI-Io. '573,618, how abandolled,and ap'plic a Saar N6.""5 93;3'64, new a andonefd, "were conrlnnedin acontinuation-in-part applicat'idn andjissuedafPatent No. 25 961405.

i "It is object, of Hej'resent invention to provide anew processforhthefpermaiient" deformation of keratinous fib rs a mare al 'q'ffh eh s; i 1 perature, in asimpleandfrl able manner and withini 'a and fafvt b j'm ie as ..A ,d iis, .t a saai y fi fl e af 1 or tlrel'ideforii la'tion'of keratinous fibers,"

hair orother 'fibers to a desiredi c'onfiguration an composition,owingjs composition toiacton the hair for {at least ts Patented May9,1961

ice

which shows that the reducing power of one mole of an alkali metalborohydride MeBH (wherein Me is the alkali metal) is theoretically fourtimes that of onemole of an alkali metal sulphite Me SO when thereducing power is calculated in gram-atoms of active hydrogen. Whilsttheinventionis not to be regarded as restricted to any theoreticalexplanationof reduction ,of the disulphide bridges of keratin or, moregenerally, with regard to the softening action exerted on the hair bysuch mix- 'tures of sulphite and borohydride, it is believed possible 7that thesulphite, in the presence of the keratin of the hair,

- the borohydride and probable by-products of the reaction,

constitutes a redox system, that is to say functions as an intermediatebetween the borohydride and the keratin. In this way the waste of.borohydrides as a result of the evolution of nascent hydrogen andthe'rapid elimination of the latter by conversion into molecularhydrogen, such as occurs when a borohydride is used; as a sole reducingagent, is avoided. Due .to the presence of sulphite, the whole ofthe'reducing. power of. the composition is as it were conveyed to thehair through the non volatile compounds such as the sulphite and other:related reducing agents which derive thereof and which contain sulphurin a vicinal oxidation stage. In an intentionally simplified example, itmay beiassumednthatta quantity of sulphite reducesv the keratinwithconcomitantconversion into sulphate and that this sulphate is..instantaneously reduced back to sulphite by the nascent'hydrogen.of-the borohydride, and so on. What actually happens is PIObably morecomplex, especially in view of the many oxidation stageswheresulphurvmaybe, at leastjtheoretica'lly (sulwhenused alone. The eflect obtainedis all the more sur prising in that it isisuperior to the sumpr'theeiiects' of these jtwo reducing agents used separately. In particular,itha sbeen found that the reducing action ofthe mixture o f'sulphitean'd borohydride manifests itselffimrriediatelyj onapplication, whereaswith an aqueous solution contain ing only a borohydride, eveniif thissolution. s adjusted to a' favourable pHyaluef (9' to '10) for asteadydecomposition, there is an initial, latentperiod during 'whi ch'the reducing action is negligible; I

"In accordance: with further feature oft eirivention,

'larly'livejhun an'fhair,"which comprises applying wine I 7 hair or sreamers, hernia and/ or after constraining-the ,permanent deformation of'hair isl'ih'u's definitely more" etfectiveathan the known processes, inwhich ionly sullphites :or borohydrides are'employed. vApart from *the iart c lar y 'tn ked esu s :Qb inedA nJR Q t Qs"th sw ur,'periorityjhas-been verified "by;.taking;asa basis of 'comp nrth pe c ne of e systin ag be r p i asca function-mike duration of cori c -vThispercentage a ,70" mirlute'sand thereafter rins ng, fix ng and J{penetrating and/ on swelling agents, kno'wnfper se for proving theeffectivenessof the conventionalpreparations for permanent waving, areadded to thecomposition. V

.thisiway an even more completeband jefiective utilizat on of thereducingproperties of the,sulphite borohydrideassociation is obtainedTheimprovement thus afforded'is rmuch. .greatefirgthafn that resulting:troin theadditiGnQOf these same penetration and/ or ,swe'llin'g agentsto a composition containing lsolely sulphites .or solely, borohydrides.The process according to the invention foreifectingthe 3. was determinedphoto colorimetrically by the method of Folin et a1. by means ofphospho-tungstic acid (J. Biol. Chem vol. 112 1935), p. 683,, andBulletin de lInstitut Textile 'de France; vol. 30 (1952), pp. 255-271):The tests were carried out on hairs of medium textu'r'etaken from a samesubject, shampooed, rinsed anddried. Each test consists of treating onetress weighing 1.25 g. with cc. of reducing solution at a temperature of20 C. for 20 minutes. The compositions of the solutions employed in eachof these tests, in which the proportions are expressed ingrarnsper 100cc. of solution, are as follows:

It willl be noted that iefau these tests, involving we same sulphite andthe' same borohydride merely with" ja view to facilitating thecompan'sb'ii, the same "r 'e'actafnt sw n .i nt isr Pr ms centage,oflcystinelinkagesbeing split bythe twor'educing 1 1.2". a Reduction,Percent... 13 a 9 1 d 9 3 (Extreme .values me m-e V 10. 3- 1:2Penetratln and swel- 1-. 1 t a Pg mmnfs 15%ethanol and i .1. t i12%lurea..

table clearlyshows that mixtures of the two reducing agents-{tests Candiexert a much greater reducingaction than the su'mdf their rediibing'actions when a som TestA: V 1 G. Sodium sulphite 2 Glycine. 2 Water tomake .100 cc.

TestB:. t

.Sodium borohydride .2 Glycine 2 Water to make 100 cc. I

Test CL. e a H Sodium sulphite 2 Sodium borohydride 2 d Glycine a 2Water to make 100 cc. l I

Test D: a 1

' Sodium sulphite Y 2 Glycine 2 Urea 12 Ethanol i v 15 Water to make 1000c. t t t y TestE: j

a Sodium borohydride 2 a Water to make 100 cc. f.

Test Fa, w a M Glycine 3 W J2 Urea a A a .12 Ethanol i i 1 i t 1 15Water to make 100 cc. 1 1 t i tory results underthe}aforesaidfionditions,

w 19 p ese v nt n was T e pro according qt etinve ta l o nQQth s k ha d.9 1 a sflm t- :after they are wound. Ihes olutionh act for: a period oftime necessary or tliesofiteningof the ham generally, 15am 45.: minutesmnd 11h? h 'zti values (9.0 to 9.3, i.e. moderately alkaline as-comparedwith the usual methods of cold-waving), the addition of penetrating andswelling agents, such as ethanol and urea, does not substantiallyimprove the action of the sulphite or borohydride when used separatelyas reducing agents (compare the reduction percentages in columns D andEof the table with those in columns A and-B), but does very substantiallyincrease the efiicac'y of the mixture of the two reducing agents(comparef the reduction percentage in column F of the table with thatinicolumn C).

Suitable water-soluble sulphites Having an alkaline reaction for use inthe process of the presentinvention' are, for example, sodium sulphite,potassium sulphite and the sulphites of nitrogenous organic bases, suchas triethanolamine sulphite, morpholine sulphite land guam'dine sul- P ta 1 r 1.

In effecting control of the pH-value of the solutions, it was foundpreferable to restort to buffers or compounds, such as weak acids,which, are capable under theconditions in which they are employed offo'rm'ing buffered systems. These include, for example. boric acidaloneor mixedwith calcium chloride, tartaric acid, citric acid, lactic acid,di-hydrogen ortho-sodium phosphate, glycine", sarcosine and taurine. Ithas also beenfoimd that itjmay be advantageous to start the treatment inthe presence of a small quantity of the weak acid 'and toadd a furtherquantity of the same acid in the course of thetreatrr ient, by sprayingor by any other: suitableimeans'. f Y

The agents promoting the penetr mnet nereactants into the hair, and theuse'of which naqsrmgeaaawmage; ous for carrying out the process"according 'to the invention, include those already'proposed forpermanent w v ing by means of sulphites, especiallyflower nconbrmuch asethanol and isopropanol, the 'glycbls others or etheresters of glycols,such'as ethylene-glycol," diethyl ene g'lyco L the monoethyl andmonobutylkthersipfjethyleh" glycol, the acetate of ethylenglycol.mbdetnyt etheif," 'nfil larly advantageousmethod ofcarrying'outthepentlin;

vention conslsts in preparing the-aqueouscomposition by dissolutionof amixture obtained'in'accordance with the process described iniapplication"Ser NOZ 573,618 and wherein the binder orcarrier ,forthejborohydride powder also acts as a penetratingfagenti "Aneiample ofswa a bin r i a l q d n a l f th ls re-awn 11,5149. a.

sition suitable .for* carrying out l k ellpijoce s to invention, hi s msitiqn c t ris n m fi l mixturepf a,water-soluble em hases alii'i resodium and/or potassium borohydxide weak acid, all uniformly embedded hs o i solidafu s a We -w g $4? t em l e t 14 2 9Fm fl9i i 9 n t ti ss.and use, said;oomposition.containjngone, mole of .p ta p lr mo s tp etz b v, i-f4i l f' hydride Such a compositipnlcan M ample, according tothe processdesc d" ,SerytNo. 573,618.21

.thidurea, formamide andacetam A q y ui t s s i a y ths n u tqhsi q sf vg, t e hair es csaflQWQ tLfiMQtlI sui abl .shape gand d1mens1ons.,; Thetresses e itnptgegpated with the, reducing 'solutionjimrnediatelbetorey and/or Al en allowed.

under, substantially the same conditions of initial =pH- 75, then rinsedand fixed in the usual manner forieaample-by sodium hq phyfl idem Aydrous. d llfill p i i :1' G ci e, Et anol--- Urea jjThehair isimmediately woundon eurlers; A fter a period of: contactfofr 1 minutes;a solution of -1 .5 g. of

glycine in 20 cc. of water is sprayed onto the hair. After r a furtherminutes, the hair isrinsed with water, fixed with a 2% hydrogen peroxidesolution and dried. A tight anddurable' curl is obltain'ed; I t I Whatwe claim is: :2 p u a 1. A method of permanently reshapmg human hairandother. keratinous ,.fibers..whicl1 .cOinpi'iss holding the fibers indesired shape .whileithey are wettedawith a hair, Softening-.so1utiont..adjusted to 7a.. pH-value N within the range of about.9.0--to-10.0.tanddcontainingflat least one hydride of a molecularweight higher-than 35Iin a ratio of one mole of sulphit e to 1 moles ofborohydride, the total quantity oftbothfrea'ctants being such a s toamount to a concentration of active Hydrogen theoretically avail able ofnot more than#2=;grams per 100 of the hairsoftening solution, allowingsaid solution toremain in contact with'th' fibers rb'rat least 15ii1inutes'; and thereafter rinsing, 's'ettiiig' by tfeat'ing with anoxidizing a ent, releasing and drying the fibers. I Y t ,1 2; method-ofpermanently. reshafiin and-otherkeratinous fibers according to*clairnl', yvhe I the -water=solublesulphitrandthe alkali metal bo hy 'drideare "used" in a ratio' 'of "one' mole of *sulphite t moles-of"borohydrider 3. Amethod of permanently reshapin' g hair and a otherkeratinous fibers which compriseshjoldin'g? thetttfib'ers indesiredishap'e while they are'wett'ed withla hair-soften"- ing solution;buffered to a pH-value within the range :of about 9.0 to 10.0 andcontaining atleast one Iwate'r-s'oluble sulphite and at least-tonerallgali metal borohydride of a molecular weight higher than in a ratio01:: one mole of *sulphite to l- 20 moles of borohydi'i de, the total''quan .tity of both reactants, being suchas,to amoi1i1f to a"concentration of active hydrogen theoretically available of Shot more than-2 gramspen 100 00. of the "hai'r soft'ening solution, allowing-saidsolution-to ren'iain' in contact with the fibers for: at least-15minutes, and thereafter rinsing, setting by treating with anoxidizing-agent;releasing and d fih sq jw e fir fit imi h ir h estua eth d nath 'q a sali l tisn." '1 Y, s ws d qia PE lue the swfiaebs tzstQJ Q-aiQ'Q/and ssm in 'sat one water-soluble sulphite and at leastorie alkali metal water-solublemsulphite-and-vat least "one alkalitmetalborodrying the fibers.

"Hume a ey ar wetted with a,hair

r 1" borohydride of a moleemasweigm higher than 35 in a sk ds. 9 Wa t.uagt tya iflqth ,e a :l eing such s p t to amount to a concentration ofactive hydrogen theoreti- I cally available of not more than 2 grams percc of f the "hairasoftening solution; "allOWlllglSQald 1 solution inainirr-contact'with the fibers'ifor at"least' 15' farnbient "temperature'while'the "pH' is maintain'e:d'esiredwalue""by'addition-ofa"'compoundselected ro theclassconsisting'ofboric'acid; tartaric acidglacti citric acid, glycine,sarcosine and? rinsing,zsetting by-tieating ingEand dr ing tHe fibers. it t; 5.:A imethod bf permanently -reshapinghiimmhairand other keratinousfibers iwhich -coniprises holding the fibers trogenou's organic basesand at leasftoneg metal bojrohy dride of ;a. molecular weight higher;'in a ratio of lane mole of, "sulphite to, 11-20, moles er horohyidride, the total quantity of qboth type's of reactants being such as toamounttto a concentration of active, hydrogen theoretically available'of not more-than) g'rams per 10 0 cc. of the hair-softening solution,allowingtsaid solution to remain in contact with thefibers for ,at least1; minutes at, ambient temperature, and, thereafterrinsing, setting bytreating with an oxidizing agent, releasing and 6. A method forpermanentlyireshaping human hair and otheri-keratinous fiberswvhichcomprises holdingithe fibers laureates-snaps while they arewetted with ahair'- softening solution adjusted to a pH-value within the range ofabout..9..0 to 10.0 .containing at least one ,water soluble. sulphite,,at least "one alkali, metal. borohydride of aimolecular; weight nhigher than t .35 ,in a "ratio. of. :one mole of sulphite to 1-20 molesofaborohydride; and a penetrationagent selected-from the class;consisting of lower v t'atty'ia lcrbliols; 'glycols; glycol] etheis;glycol ether estersfcyclic ethers'anfd ethylene oxide polycondnsates',the total quantity ofthi reducing agents'beingsucli 'as to amount to aconcentration of active hydrogen theoretisa x v il blelpfi mt mvrs 111;; :sx m r str msof th mh inqits ms s t nsel nst at .=s9lv iontqreinain in contact with the fibers for at least liminutes at ambienttemperature, and thereafter rinsing, setting by t atmentstqsidisi zsa easin and-d y n h fibers.

theoretically available of not more than 2 grams 365 100 gtthehair-softening solution, allowinggsaid solution one mole of sulphite tol1-fl20. moles of borohydride, the 5917-1 gantit rot h Mus n agents b iamount 'to" a "conntratidn 6f grams per 1 giis'soliltron 'of a we'a'liorganie' acid, tt g posfi'r' waiameninfifi m 9. In a mth'od'ofpermanently reshaping human hair and othri kei atinous fibers by holdingthe' fiBIrQ "desird s'hape wliile they afe watt ed'with an aqlieoiiihairsoftening solution adjusted to a pH-value within the range of about 9.0to 10.0 containing at least one Watersoluble sulphite, at least onealkali metal borohydride of a molecular weight higher than 35 in a ratioof one mole of sulphite to 1-20 moles of borohydride and an acidcompound selected from the class consisting of boric acid, tartaricacid, lactic acid, .citric acid, glycine, sarcosine and taurine, thetotal quantity of the reducing agents being such as to amount to aconcentration of active hydrogen theoretically available of not morethan 2 grams per 100 cc. of the hair-softening solution and the timeallowed for said solution to remain in contact with the fibers being ofat least 15 minutes at ambient temperature, the step which compriseskeeping apart substantially half the amount of said acid compound andapplying it to the fiber about minutes later.

10. A method of permanently reshaping human hair and other keratinousfibers which comprises holding the fibers in desired shape while theyare wetted with an aqueous hair-softening solution bufiered to apH-value within the range of about 9.0 to 10.0 containing at least oneWater-soluble sulphite, at least one alkali metal borohydride of amolecular weight higher than 35 in a ratio of one mole of sulphite to1-20 moles of borohydride, a water miscible penetrating agent selectedfrom the class consisting of lower fatty alcohols, glycols, glycolethers, glycol ether-esters, cyclic ethers and ethylene oxidepolycondensates and a water soluble hair swelling agent selected fromthe class consisting of urea, thio-urea, formamide, acetamide andcarboxylic acid amides of organic heterocyclic nitrogenous bases in anaqueous medium, the total quantity of the reducing agents being such asto amount to a concentration of active hydrogen theoretically availableof not more than 2 grams per 100 cc. of the hair-softening solution,allowing said solution to remain in contact with the fibers for at leastminutes at ambient temperature, and thereafter rinsing, setting bytreating with an oxidizing agent, releasing and drying the fibers.

11. A solid hair waving composition to be used in aqueous solution whichcomprises a pulverulent mixture of a water-soluble sulphite, an alkalimetal borohydride of a molecular weight higher than 35 and a crystallineweak acid, all uniformly embedded as a stable dispersion in a solid,fusible and water-miscible carrier which is chemically inert undernormal conditions of storage and use, said composition containing onemole of sulphite to 1-20 moles of borohydride and a suitable amount ofthe weak acid to ensure a pH-value of 9-10 in the solution ready foruse.

12. A solid hair waving composition according to claim 11 wherein thesolid, fusible and water-miscible carrier is present in the proportionof at least percent of the composition.

13. A solid hair waving composition to be used in aqueous solution whichcomprises a pulverulent mixture of a water-soluble sulphite, an alkalimetal borohydride of a molecular weight higher than 35 and a crystallineweak acid, all uniformly embedded as a stable dispersion in a waxypolycondensate of ethylene oxide, said composition containing one moleof sulphite to 1-20 moles of borohydride and a suitable amount of theweak acid to ensure a pH-value of 9-10 in the solution ready for use.

14. A solid hair waving composition to be used in aqueous solution whichcomprises a pulverulent mixture of a Water-soluble sulphite, an alkalimetal borohydride selected from the class consisting of sodiumborohydride and potassium borohydride and a crystalline weak acid, alluniformly embedded as a stable dispersion in a polycondensate ofethylene oxide of an average molecular weight higher than 1500, saidcomposition containing one mole of sulphite to 2-4 moles of borohydrideand a suitable amount of the weak acid to ensure a pH-value of 9-10 inthe solution ready for use.

References Cited in the file of this patent UNITED STATES PATENTS2,351,718 Speakman June 20, 1944 2,464,280 Reed Mar. 15, 1949 2,766,760Bogaty Oct. 16, 1956 FOREIGN PATENTS 75,921 Netherlands Sept. 15, 1954OTHER REFERENCES Speakman: J. Soc. Dyers and Colorists, vol. 52, 1936,pp. 335-346.

1. A METHOD OF PERMANENTLY RESHAPING HUMAN HAIR AND OTHER KERATINOUSFIBERS WHICH COMPRISES HOLDING THE FIBERS IN DESIRED SHAPE WHILE THEYARE WETTED WITH A HAIRSOFTENING SOLUTION ADJUSTED TO A PH-VALUE WITHINTHE RANGE OF ABOUT 9.0 TO 10.0 AND CONTAINING AT LEAST ONE WATER-SOLUBLESULPHITE AND AT LEAST ONE ALKALI METAL BOROHYDRIDE OF A MOLECULAR WEIGHTHIGHER THAN 35 IN A RATIO OF ONE MOLE OF SULPHITE TO 1-20 MOLES OFBOROHYDRIDE, THE TOTAL QUANTITY OF BOTH REACTANTS BEING SUCH AS TOAMOUNT TO A CONCENTRATION OF ACTIVE HYDROGEN THEORETICALLY AVAILABLE OFNOT MORE THAN 2 GRAMS PER 100 CC. OF THE HAIRSOFTENING SOLUTION,ALLOWING SAID SOLUTION TO REMAIN IN CONTACT WITH THE FIBERS FOR AT LEAST15 MINUTES, AND THEREAFTER RINSING, SETTING BY TREATING WITH ANOXIDIZING AGENT, RELEASING AND DRYING THE FIBERS.